Methyl 3-amino­but-2-enoate

Wang, X.; Zhang, L.-Z.

doi:10.1107/S160053681202288X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1930

doi:10.1107/S160053681202288X

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Methyl 3-aminobut-2-enoate

Xiao Wang ^a ^* and Li-Zhu Zhang ^a

^aDepartment of Applied Chemistry, Harbin Institute of Technology, Harbin, Heilongjiang 150001, People's Republic of China
^*Correspondence e-mail: wangx8000@sina.com

(Received 10 May 2012; accepted 19 May 2012; online 31 May 2012)

The title compound, C₅H₉NO₂, is almost planar (r.m.s. deviation for the non-H atoms = 0.036 Å) and an intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, N—H⋯O interactions link the molecules into C(6) chains propagating along [010].

Related literature

For further synthetic details, see: Rakshit et al. (2010 ); Vanden Eynde et al. (1995 ).

Experimental

Crystal data

C₅H₉NO₂
M_r = 115.13
Monoclinic, P 2₁ /c
a = 8.3020 (12) Å
b = 9.7232 (14) Å
c = 7.665 (1) Å
β = 97.855 (13)°
V = 612.93 (15) Å³
Z = 4
Cu Kα radiation
μ = 0.81 mm⁻¹
T = 113 K
0.18 × 0.16 × 0.10 mm

Data collection

Rigaku Saturn944 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ) T_min = 0.868, T_max = 0.924
6605 measured reflections
1175 independent reflections
1019 reflections with I > 2σ(I)
R_int = 0.071

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.141
S = 1.20
1175 reflections
84 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.84 (2)	2.05 (2)	2.8778 (16)	168.9 (19)
N1—H1B⋯O1	0.89 (2)	2.08 (2)	2.7168 (16)	127.7 (15)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681202288X/hb6788sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202288X/hb6788Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202288X/hb6788Isup3.cml

checkCIF report

Comment top

Nifedipine was found to be a highly effective calcium antagonist. Consequently,many compounds which were similar in structure to nifedipine have already been used as therapeutic agents for treatment of cerebral circulatory disorder,hypertension and so on. The title compound (I) is an intermediate for the synthesis of this family of compounds and its structure is reported here. As shown in Fig. 1, in each molecular unit, almost non-hydrogen atoms in the same plane, and the deviation is 0.036 nm. The length of the double bond is slightly longer than the normal double bond of ethylene likewise, the bond between carbon and nitrogen are shorter than normal C—N bond. A short intermolecular N—H···O interaction (Table 1) occurs [symmetry code:(i)-x + 1,y - 1/2,-z + 1/2], and relatively strong intramolecular N—H···O hydrogen bonds also exists.

Related literature top

For further synthetic details, see: Rakshit et al. (2010); Vanden Eynde et al. (1995).

Experimental top

Impoved from the published methods by Rakshit et al. (2010) and Vanden Eynde et al. (1995) a modification of the synthetic procedure was used to prepare the title compound from methyl acetoacetate and ammonium acetate. Colorless prisms of (I) were obtained by recrystallizing from a ethyl acetate solution. mp: 355 K. Analysis, calculated for C₅H₉NO₂: C 52.16, H 7.88, N 12.17; found: C 52.15, H 7.87, N 12.16.

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram for (I).

Methyl 3-aminobut-2-enoate top

Crystal data top

C₅H₉NO₂	D_x = 1.248 Mg m⁻³
M_r = 115.13	Melting point: 355 K
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54187 Å
a = 8.3020 (12) Å	Cell parameters from 670 reflections
b = 9.7232 (14) Å	θ = 27.9–71.6°
c = 7.665 (1) Å	µ = 0.81 mm⁻¹
β = 97.855 (13)°	T = 113 K
V = 612.93 (15) Å³	Prism, colorless
Z = 4	0.18 × 0.16 × 0.10 mm
F(000) = 248

Data collection top

Rigaku Saturn944 CCD diffractometer	1175 independent reflections
Radiation source: fine-focus sealed tube	1019 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.071
Detector resolution: 14.629 pixels mm^-1	θ_max = 71.9°, θ_min = 5.4°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −11→9
T_min = 0.868, T_max = 0.924	l = −9→9
6605 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.141	w = 1/[σ²(F_o²) + (0.0954P)²] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max < 0.001
1175 reflections	Δρ_max = 0.36 e Å⁻³
84 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.32 (2)

Crystal data top

C₅H₉NO₂	V = 612.93 (15) Å³
M_r = 115.13	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 8.3020 (12) Å	µ = 0.81 mm⁻¹
b = 9.7232 (14) Å	T = 113 K
c = 7.665 (1) Å	0.18 × 0.16 × 0.10 mm
β = 97.855 (13)°

Data collection top

Rigaku Saturn944 CCD diffractometer	1175 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	1019 reflections with I > 2σ(I)
T_min = 0.868, T_max = 0.924	R_int = 0.071
6605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.36 e Å⁻³
1175 reflections	Δρ_min = −0.51 e Å⁻³
84 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.36825 (11)	0.18110 (10)	0.32340 (12)	0.0327 (4)
O2	0.12958 (12)	0.21372 (10)	0.42596 (13)	0.0357 (4)
N1	0.45092 (13)	−0.08490 (14)	0.27315 (14)	0.0320 (4)
C1	0.24663 (14)	0.13160 (14)	0.37507 (15)	0.0279 (4)
C2	0.21064 (14)	−0.01182 (15)	0.38684 (15)	0.0294 (4)
H2	0.1142	−0.0387	0.4317	0.035*
C3	0.31094 (14)	−0.11148 (14)	0.33542 (15)	0.0285 (4)
C4	0.26670 (18)	−0.26132 (15)	0.34523 (18)	0.0348 (4)
H4A	0.2644	−0.3035	0.2288	0.042*
H4B	0.1592	−0.2697	0.3836	0.042*
H4C	0.3477	−0.3083	0.4297	0.042*
C5	0.15619 (19)	0.35898 (16)	0.4094 (2)	0.0400 (5)
H5A	0.2563	0.3854	0.4849	0.048*
H5B	0.0641	0.4096	0.4455	0.048*
H5C	0.1663	0.3810	0.2866	0.048*
H1B	0.487 (2)	0.002 (2)	0.269 (3)	0.048 (5)*
H1A	0.515 (2)	−0.147 (2)	0.249 (2)	0.046 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0298 (6)	0.0295 (6)	0.0403 (6)	−0.0019 (4)	0.0102 (4)	−0.0002 (4)
O2	0.0328 (6)	0.0327 (7)	0.0437 (6)	0.0049 (4)	0.0128 (4)	−0.0031 (4)
N1	0.0287 (6)	0.0280 (8)	0.0409 (7)	0.0012 (5)	0.0109 (5)	−0.0021 (5)
C1	0.0263 (6)	0.0312 (9)	0.0262 (6)	0.0009 (5)	0.0040 (5)	−0.0015 (5)
C2	0.0259 (6)	0.0325 (9)	0.0311 (7)	−0.0039 (5)	0.0080 (5)	−0.0006 (5)
C3	0.0299 (7)	0.0301 (8)	0.0252 (6)	−0.0030 (5)	0.0024 (5)	−0.0002 (5)
C4	0.0423 (8)	0.0294 (8)	0.0335 (7)	−0.0043 (6)	0.0078 (6)	−0.0007 (5)
C5	0.0457 (8)	0.0316 (9)	0.0436 (8)	0.0095 (6)	0.0097 (6)	−0.0031 (6)

Geometric parameters (Å, º) top

O1—C1	1.2317 (16)	C2—H2	0.9500
O2—C1	1.3557 (15)	C3—C4	1.5069 (18)
O2—C5	1.4379 (18)	C4—H4A	0.9800
N1—C3	1.3404 (17)	C4—H4B	0.9800
N1—H1B	0.89 (2)	C4—H4C	0.9800
N1—H1A	0.84 (2)	C5—H5A	0.9800
C1—C2	1.432 (2)	C5—H5B	0.9800
C2—C3	1.3702 (19)	C5—H5C	0.9800

C1—O2—C5	115.36 (11)	C3—C4—H4A	109.5
C3—N1—H1B	120.4 (12)	C3—C4—H4B	109.5
C3—N1—H1A	123.3 (14)	H4A—C4—H4B	109.5
H1B—N1—H1A	115.8 (18)	C3—C4—H4C	109.5
O1—C1—O2	120.91 (13)	H4A—C4—H4C	109.5
O1—C1—C2	126.03 (12)	H4B—C4—H4C	109.5
O2—C1—C2	113.05 (11)	O2—C5—H5A	109.5
C3—C2—C1	122.04 (12)	O2—C5—H5B	109.5
C3—C2—H2	119.0	H5A—C5—H5B	109.5
C1—C2—H2	119.0	O2—C5—H5C	109.5
N1—C3—C2	123.82 (13)	H5A—C5—H5C	109.5
N1—C3—C4	115.67 (12)	H5B—C5—H5C	109.5
C2—C3—C4	120.50 (12)

C5—O2—C1—O1	1.92 (16)	O2—C1—C2—C3	177.61 (10)
C5—O2—C1—C2	−177.39 (11)	C1—C2—C3—N1	1.13 (19)
O1—C1—C2—C3	−1.7 (2)	C1—C2—C3—C4	−178.35 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.84 (2)	2.05 (2)	2.8778 (16)	168.9 (19)
N1—H1B···O1	0.89 (2)	2.08 (2)	2.7168 (16)	127.7 (15)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₉NO₂
M_r	115.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	8.3020 (12), 9.7232 (14), 7.665 (1)
β (°)	97.855 (13)
V (Å³)	612.93 (15)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.18 × 0.16 × 0.10

Data collection
Diffractometer	Rigaku Saturn944 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2009)
T_min, T_max	0.868, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	6605, 1175, 1019
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.141, 1.20
No. of reflections	1175
No. of parameters	84
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.51

Computer programs: CrystalClear (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.84 (2)	2.05 (2)	2.8778 (16)	168.9 (19)
N1—H1B···O1	0.89 (2)	2.08 (2)	2.7168 (16)	127.7 (15)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Science and Technology Fund of Tianjin Province, China, for financial support (No. 10ZCKFSH00500).

References

Rakshit, S., Patureau, F. W. & Glorius, F. (2010). J. Am. Chem. Soc. 132, 9585–9587. Web of Science CrossRef CAS PubMed Google Scholar
Rigaku (2009). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vanden Eynde, J. J., Mayence, A., Lor, P. & Van Haverbeke, Y. (1995). Bull. Soc. Chim. Belg. 104, 387–392. CAS Google Scholar